CN103399070A - Preparation method of high-sensitivity electrochemical sensors for glucose detection based on nickel hydroxide and glucose oxidase - Google Patents
Preparation method of high-sensitivity electrochemical sensors for glucose detection based on nickel hydroxide and glucose oxidase Download PDFInfo
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- CN103399070A CN103399070A CN2013103545744A CN201310354574A CN103399070A CN 103399070 A CN103399070 A CN 103399070A CN 2013103545744 A CN2013103545744 A CN 2013103545744A CN 201310354574 A CN201310354574 A CN 201310354574A CN 103399070 A CN103399070 A CN 103399070A
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Abstract
In a sensor prepared by using the method disclosed by the invention, a Ni(OH)2 deposited chitosan-gold nanoparticle composite film not only serves as an electrochemical redox couple probe, but also serves as a matrix which fixes glucose oxidase and can keep the activity of the glucose oxidase. A Ni2+/Ni3+redox couple and glucose oxidase are successfully combined together, thereby realizing the high-sensitivity detection on glucose. The chitosan-gold nanoparticle composite film as the biological matrix not only provides a platform for the formation of Ni(OH)2, but also is a medium for electron transfer between glucose and an electrode, and the Ni(OH)2 and chitosan-gold nanoparticle composite film provides a platform for the existence of active enzymes.
Description
Technical field:
The present invention relates to a kind of preparation of the electrochemical sensor for glucose detection, relate in particular to a kind of preparation method of the novel electrode based on nickel hydroxide and glucose oxidase.
Background technology:
The sensitive and accurate detection of concentration of glucose has very important effect in cardiopathic Clinics and Practices, clinical diagnosis biological chemistry, wastewater treatment and food industry.High sensitivity, reliability, device simply, at a low price, superior compatibility, miniaturization the characteristics such as arrange and make electrochemical techniques become very important instrument in detection method.Research mainly concentrates on the current mode glucose sensor, and the catalytic action that this class sensor mainly is based on glucose oxidase is conversion of glucose gluconolactone.Although this method provides very large selectivity, the surface that directly enzyme is fixed on electrode can cause the forfeiture of enzymatic activity.The major defect of the method for having reported is exactly the difficult problem that between glucose oxidase and electrode, electronics transmits, because flavin adenine dinucleotide (FAD) (coenzyme) is protected by one deck protein shell dearly.Now, the non-enzymatic glucose sensor based on the direct electrochemistry oxidation of electrode surface glucose has received the very large concern of researcher.A series of metal (platinum, palladium, gold, nickel and copper) nano structural material, and alloy (platinum-nickel, platinum-Jin), and metal oxide has been widely used in the direct oxidation of glucose.Wherein, Ni (OH)
2The existence of/NiOOH redox couple makes the nano material based on nickel show unsurpassed activity.Various strategy,, as NiO being deposited on multi-walled carbon nano-tubes (MWCNT), be distributed to nano nickel particles on Graphene, the NiO nanofiber dripped on the glassy carbon electrode of graphene oxide modification, has been used to the traditional electrode of modification.But the instability and the redox couple that apply catalytic membrane under electromotive force make this technology still have very large challenge to weakening of electronics transmission between metal electrode.
Remarkable biocompatibility and biodegradable performance make shitosan become and build very attractive material in amperometric biosensor.The filming performance of shitosan makes it be widely used for the large molecule of fixed biologically in research in recent years.Such as, the chitosan-metal nanoparticle composite film has just demonstrated extraordinary electric transmission efficiency in the detection of heavy metal ion.
Summary of the invention:
The present invention relates to a kind of high sensitive electrochemical transducer production method that is used for glucose detection based on nickel hydroxide and glucose oxidase.
A kind of high sensitive electrochemical transducer production method that is used for glucose detection based on nickel hydroxide and glucose oxidase, its step is as follows:
(1) preparation of shitosan gold nano compound substance (CGNC): at first prepare 2～5% chitosan solution in 2% acetic acid solution; Then add the chlorauric acid solution of 6～10mol/L and constantly stir in above-mentioned chitosan solution, the volume ratio of chitosan solution and chlorauric acid solution is 1: 1～1: 3; The mixed solution that obtains continues to stir 1～1.5h after stirring after 2～3h the ice-water bath sodium borohydride that dropwise adds again 3～10mL25～35mmol/L.The solution centrifugal that obtains obtains washing and obtaining sample with acidic aqueous solution after the CGNC particle.
(2) preparation of novel electrode: before carrying out the surface coating, then gold electrode first uses the alumina powder polishing of 3.5～6.0 μ m with the emery paper polishing, then with ultrapure water, cleans.Then electrode is immersed in Piranha solution (30% hydrogen peroxide: the concentrated sulphuric acid=1: 3, V: process in deionized water for ultrasonic after 15～25min V), finally with ethanol washing drying of new preparation.The CGNC film deposits on gold electrode by the method for electro-deposition.Two clean gold electrodes are immersed in liquid CGNC solution and connect the direct supply of 3V.It doesn't matter to find the thickness of CGNC film and the concentration of shitosan in research, and with sedimentation time, direct relation is arranged, so change the thickness of electrode surface CGNC film by changing sedimentation time.After deposition, electrode takes out and with deionized water, washs dry a whole night in exsiccator afterwards.Then, carry out the deposition 2～3min of metallic nickel in the nickel chloride solution at 5.5～6.5mmol/L under the electromotive force of 0.9V.Metallic nickel carries out cyclic voltammetry scan to the oxidation of nickel hydroxide in the potential range of 0.2～0.6V realizes for 45～65 times by the sweep speed with 100mV/s.Glucose oxidase is fixed to Ni (OH) by the method for physisorption
2Just obtained novel electrode Au/CGNC/Ni (OH) behind the surface of film
2/ GO
x
In the sensor that the present invention relates to, Ni
2+/ Ni
3+Thereby redox couple and glucose oxidase are realized the highly sensitive detection to glucose by successfully combining.Shitosan-gold nano grain laminated film, as a kind of biological substrate, is not only Ni (OH)
2Formation platform is provided, and be a kind of medium that between glucose and electrode, electronics transmits.Ni (OH)
2And shitosan-gold nano grain composite membrane provides platform for the existence of organized enzyme.
Embodiment:
In order to deepen the understanding of the present invention, the invention will be further described below in conjunction with implementing.
A kind of preparation method of the high sensitive electrochemical sensor that is used for glucose detection based on nickel hydroxide and glucose oxidase, its step is as follows:
(1) preparation of shitosan gold nano compound substance (CGNC): the chitosan solution of at first preparing 15mL3% in 2% acetic acid solution; Then add the chlorauric acid solution of 30mL6mol/L and constantly stir in above-mentioned chitosan solution; The mixed solution that obtains continues to stir 1h after stirring after 2h the ice-water bath sodium borohydride that dropwise adds again 3mL30mmol/L.The solution centrifugal that obtains obtains washing and obtaining sample with acidic aqueous solution after the CGNC particle.
(2) preparation of novel electrode: before carrying out the surface coating, then gold electrode first uses the alumina powder polishing of 5 μ m with the emery paper polishing, then with ultrapure water, cleans.Then electrode is immersed in Piranha solution (30% hydrogen peroxide: the concentrated sulphuric acid=1: 3, V: process in deionized water for ultrasonic after 20min V), finally with ethanol washing drying of new preparation.The CGNC film deposits on gold electrode by the method for electro-deposition.Two clean gold electrodes are immersed in liquid CGNC solution and connect the direct supply of 3V.It doesn't matter to find the thickness of CGNC film and the concentration of shitosan in research, and with sedimentation time, direct relation is arranged, so change the thickness of electrode surface CGNC film by changing sedimentation time.After deposition, electrode takes out and with deionized water, washs dry a whole night in exsiccator afterwards.Then, carry out the deposition 2min of metallic nickel in the nickel chloride solution at 6mmol/L under the electromotive force of 0.9V.Metallic nickel carries out cyclic voltammetry scan to the oxidation of nickel hydroxide in the potential range of 0.2～0.6V realizes for 50 times by the sweep speed with 100mV/s.Glucose oxidase is fixed to Ni (OH) by the method for physisorption
2Just obtained novel electrode Au/CGNC/Ni (OH) behind the surface of film
2/ GO
x
(3) electrochemical property test: the electrochemical property test of prepared electrochemical sensor carries out on electrochemical workstation (CH Instruments, Austin, Texas).Three-electrode system: the modification gold electrode is as working electrode, and the platinum line is as auxiliary electrode, and saturated calomel electrode is as reference electrode.Electrochemical measurement is at room temperature carried out with the sweep speed of 100mV/s.
In the prepared sensor of the present invention, the shitosan of Ni (OH) deposition-gold nano grain laminated film not only as a kind of electrochemical redox to probe, and as a kind of matrix fixing glucose oxidase and can make it keep active.Electrochemical property test shows that prepared novel sensor has low detectability (100 * 10 to the detection of glucose
-9Mol/L), wide detectability (1～100 * 10
-6Mol/L) and have very high sensitivity (16840 μ A mmol/L/cm
2).
Claims (3)
1. the high sensitive electrochemical transducer production method that is used for glucose detection based on nickel hydroxide and glucose oxidase, is characterized in that, step is as follows:
(1) preparation of shitosan gold nano compound substance: at first prepare 2～5% chitosan solution in 2% acetic acid solution; Then add the chlorauric acid solution of 6～10mol/L and constantly stir in above-mentioned chitosan solution; The mixed solution that obtains continues to stir 1～1.5h after stirring after 2～3h the ice-water bath sodium borohydride that dropwise adds again 3～10mL25～35mmol/L; The solution centrifugal that obtains obtains washing and obtaining sample with acidic aqueous solution after shitosan gold nano composite material granular thing;
(2) preparation of novel electrode: before carrying out the surface coating, then gold electrode first uses the alumina powder polishing of 3.5～6.0 μ m with the emery paper polishing, then with ultrapure water, cleans; Then electrode is immersed in the Piranha solution (30% hydrogen peroxide: the concentrated sulphuric acid=1: 3, volume ratio) of new preparation and processes in deionized water for ultrasonic after 15～25min, dry with the ethanol washing finally; Shitosan gold nano composite material film deposits on gold electrode by the method for electro-deposition; Two clean gold electrodes are immersed in liquid shitosan gold nano compound substance solution and connect the direct supply of 3V; After deposition, electrode takes out and with after the deionized water washing in exsiccator dry 24 hours; Then, carry out the deposition 2～3min of metallic nickel in the nickel chloride solution at 5.5～6.5mmol/L under the electromotive force of 0.9V; Metallic nickel carries out cyclic voltammetry scan to the oxidation of nickel hydroxide in the potential range of 0.2～0.6V realizes for 45～65 times by the sweep speed with 100mV/s; Glucose oxidase is fixed to Ni (0H)
2Just obtain novel electrode behind the surface of film.
2. electrochemical sensor preparation method as claimed in claim 1, it is characterized in that: the volume ratio of described chitosan solution and chlorauric acid solution is 1: 1～1: 3.
3. electrochemical sensor preparation method as claimed in claim 1, it is characterized in that: described glucose oxidase is fixed to Ni (OH)
2The method of film is physisorption.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103616420A (en) * | 2013-12-05 | 2014-03-05 | 江南大学 | Photoelectrochemical determination method of glucose in serum |
| CN104777192A (en) * | 2015-03-18 | 2015-07-15 | 浙江工商大学 | Detection method of food sweetness degree |
| CN106290498A (en) * | 2016-08-08 | 2017-01-04 | 青岛科技大学 | Based on PEDOT rGO Ni (OH)2the preparation method of the glucose sensor electrode without enzyme of composite nano materials |
| CN106290517A (en) * | 2016-08-15 | 2017-01-04 | 中驭(北京)生物工程有限公司 | A kind of highly sensitive glucose is without enzyme sensor electrode material and preparation method thereof |
| CN114813870A (en) * | 2022-05-19 | 2022-07-29 | 西安交通大学 | Electrochemical glucose sensor electrode and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103616420A (en) * | 2013-12-05 | 2014-03-05 | 江南大学 | Photoelectrochemical determination method of glucose in serum |
| CN103616420B (en) * | 2013-12-05 | 2016-01-13 | 江南大学 | The Optical Electro-Chemistry assay method of glucose in serum |
| CN104777192A (en) * | 2015-03-18 | 2015-07-15 | 浙江工商大学 | Detection method of food sweetness degree |
| CN104777192B (en) * | 2015-03-18 | 2017-06-20 | 浙江工商大学 | A kind of detection method of food sugariness |
| CN106290498A (en) * | 2016-08-08 | 2017-01-04 | 青岛科技大学 | Based on PEDOT rGO Ni (OH)2the preparation method of the glucose sensor electrode without enzyme of composite nano materials |
| CN106290498B (en) * | 2016-08-08 | 2019-11-05 | 青岛科技大学 | Based on PEDOT-rGO-Ni (OH)2The preparation method of the glucose sensor electrode without enzyme of composite nano materials |
| CN106290517A (en) * | 2016-08-15 | 2017-01-04 | 中驭(北京)生物工程有限公司 | A kind of highly sensitive glucose is without enzyme sensor electrode material and preparation method thereof |
| CN106290517B (en) * | 2016-08-15 | 2018-11-02 | 中驭(北京)生物工程有限公司 | A kind of glucose of high sensitivity is without enzyme sensor electrode material and preparation method thereof |
| CN114813870A (en) * | 2022-05-19 | 2022-07-29 | 西安交通大学 | Electrochemical glucose sensor electrode and preparation method thereof |
| CN114813870B (en) * | 2022-05-19 | 2023-11-14 | 西安交通大学 | Electrochemical glucose sensor electrode and preparation method thereof |
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Application publication date: 20131120 |